Manufacture of water-insoluble monoazo-dyestuffs



United States Patent 703,319 MANUFAGTURE or whrnn ngsownm MON OAZO-DYESTUFF Ernst Fischer, Offenbach am Main, Germany, assignor to Farbwerke Hoechst A. G., yormals Meister Lucius und BruuingyErankfurt am Main Hochst, Germany, a company of Germany No Drawing. Application October 17, 1951, Serial No? 251,830

halogen which dyestufls'do nercontain any groups imparting solubility in Water afid in which x represents a substituent .of the groupvconsistingtoflalkyl and alkoxy and the henzene residues a and-b may contain further halogen atoms.

I have found that said dyestuffs can be made by coupling the diazo-compoun'dof anamine-of the general formula in which the benzene residue b may contain further halogen atoms, and sd-- choosing the) components that they contain no groups imparting solubility in water, for example; sulphonic' acid or carboxylic 1616 groups.--

0 f The-newdyestutfswyield red to -bluish-red tint's having good fasthess"properties; They are especially-suitablefor coloringplastic ma'sse's composed of organic compounds of high molecular weight, for example, formaldehyde-urea, formaldehyde-phenol or formaldehydeamine condensation, products, polyvinyl compounds, rubber and the like, and' can -alsob used for the production of dyestuff lakes which are fast to oil and light, and also, by addition to spinningE'soldtions,; for producing colored cellulose acetate and vis'cose artificial silk.

As compared with the monoazo-dyestutfs of comparable constitution described in" German specification No. 602,064, which describes no dyestutf containing in the molecule the special distribution of halogen atoms characteristic of the present inventioh,the new dyestuffs are distinguished by a specific action, which consists in that they bleed intoundyed yinyl chloride polymerization products considelabl-y'ls"'tlianthe aforsaid comparable dyestuffs.

2,703,319 Patented Mar. 1, 1955 The dyestuff may be used for coloringa polymerization product of vinylchloride in the followingmanner: parts diaper ri'z'atio'r'i pro'diic't of iiiyl'chloride' 50 parts! of phth-alieacid di-n butyl ester (acting'as a softening 'agent") p 0.3 part of titanium dioxi'd and 0.45 part of 'tl'ie'azo-dye'st'iifi are mixed togethenand then the mixture-is homogenized by means of-kneadin'ga-rollers'for 10 minutes at C There is obtained a soft rubber-like mass haying a bluisli red "coloration, which does notbleed into I the uncolored polymerization product and possesses a good-fastnessto light.- Iiis'tadof, or'in addition to, titanium dioxide the reniay be incorporated in the kneaded ma'ssanotlfignfilhngc material -of the klnd usual in wdrking' up ru er.

13.1- parts of 1-amino-2-methyl-benzene 5-carboyl 1'- ami'no-4' cliloi'obefiine are dialzotized in the-usual manner. After rendering the suspension of the-unintenpound nutral'to" Congo with' s'odium' acetate; thre' is stirred idto the suspension a solution of16. 6"parts of 1-(2--:3'-oxynaphthoylamirio)-3t 4=diclilorobeiiieiie .irif a dilute solution of caustic soda; and'then the whole' is heated to 40 C-. The-resulting red dyestufi is-sepa'rated by filtratiorigwa'shed'well and dried. It may be us'ed'in the following-manner for'coloriiig rubber. H

2 per centof the azo-dyestufiare-worked byrolling into a mixture of rubber','filli1ig material; sulphur and vulcanization"accelerator. The mass isvulcanized hot in a press, and then has a red coloration which has good fastn'ss to-light and'neithr bleeds into white'rubber nor bleeds ou't.

By 'iinme'rsing a mixtur of rubber,- an o'rdinary' fluxand 0.5 per cent of theazc'a-djiestuif in a solution of sulphur chloride in benzene, and vulcanizingin th'e'cold' there is obtained a colored mass having similar-properties;

Examples A -red dyestuff -is-pro'du'ce'd from the diazo compound from 13.9 parts-or1amino z-methexyanzeneseesaw- 1'-amino-4f-chlorobenzii 'and14.9 parts of 1-(2':3'-oxynaphthoylam'ino)+4=clilorobenzene in the manner described in Example 1 or 21 Lakes produced with the resultiiig dy'estuff yieldb'lui's'h red' tin-ts having-gem fas'tiiss to oil and light.

Thecoupling may also be carried out in the presence of a carrier suitable for making dyestufi lakes.

Example 4 A dyestufi is prepared in the manner described in Example 1 from 14.8 parts of 1-amino-2-methylbenzene-5- carboyl-1'-amino-2':4'-dichlorobenzene and 16.6 parts of 1 (2':3' oxynaphthoyl amin)-3:4-dichlorobenzene, and is a red powder which can be used for coloring in the manner illustrated in that example polymerization products of vinyl chloride in red tints which are fast to light, but which are more yellowish than those of the dyestufi described in Example 1. The color does not bleed into the undyed polymerization product.

Example By using in Example 1, instead of 14.9 parts of 1- (2:3-0Xynaphthoylamino)-4-chlorobenzene, 18.4 parts of 1 (2:3'-oxynaphthoylamino)-3:425-trichlorobenzene there is obtained a dyestufi yielding similar tints. 0.5 part of the resulting dyestutf is added to 100 parts of a condensation product of urea and formaldehyde which contains 30 per cent of wood meal as filling material, and the mixture is ground for 12 hours in a ball mill. The mass is then placed in a press in which pressing and hardening to form the desired shaped article is carried out in the course of 5 minutes at 140 C.

In the following table is given a number of further components which can be used in the present process, and

also the color of the resulting monoazo-dyestuffs, which also possess good properties of fastness.

Diem-component Azo-component Tint;

1-Amino-2-methylbenzene-5- 1- (2 3-oxynaphthoylred.

carboyl-l' -amln0 -4' -chlor0- amino) -4-chlorobenzene. benzene.

D0 1-(2:3-oxynaphthoyl- D0.

amino)-4-bromobenzene. 1-(2:3'-oxynaphthoyl- Do.

amino)-3:4-diehlorobenzene. 1-(2' 3-oxynaphthoyl- Do.

l-Amino-2-methylbenzene-5- carboyl-1'-amino-3 4- dichlorobenzene.

l-Amino-2-methylbenzene-5- dichlorobenzene. 1-Amino-2-ethoxybenzene-5- .do bluish'red.

carboyl -1 -amino -4 chlorobenzene.

1-(2':3'-oxynaphth0yl- Do.

amino)-3:4-dichlorobenzene. 1-(2':3-0xynaphthoyl- D0.

amino)-4-chlorobenzene.

1-(2:3-oxyna hthoyl- Do.

amino)-2:4-dic loroben- 1-(2 3-oxyna hthoyl- IDo.

amino)-3:4-dic orobentrichlorobenzene. zene. 1-Amin0-2-methoxybenzenedo Do.

trichlorobenzene.

1 -Amino Z-methoxybenzene- 5-carboyl-1'-amino-2' 4- dichlorobenzene.

ammo) -2:3:4-trichlorobenzene .l-Amino-Z-methoxybeuzene- 1-(2:3-0xynaphthoyl- D0.

5-earboyl-1-amino-2 :5- amino) -2:4:6-triehlorodichlorobenzene. benzene.

Do 1-(2':3-oxynaphthoyl- Do.

amino) -3 4: 5 trichloro benzene.

1-Amino-2-methoxybenzenedo D0.

4 I claim: 1. The water-insoluble monoazo-dyestufis of the following general formula:

CO.NH

CO-NH in which x represents a substituent of the group consisting of alkyl and alkoxy, y represents a substituent of the group consisting of hydrogen and chlorine and z represents a substituent of the group consisting of chlorine and bromine.

2. The water-insoluble monoazo-dyestuffs of the following general formula:

in which 1: represents a substituent of the group consisting of methyl and methoxy and y represents a substituent of the group consisting of hydrogen and chlorine.

4. The monoazo-dyestuff of the following formula:

5. The monoazo-dyestiifl of the following formula:

(JUNE 0 ONE- 6. The monoazo-dyestufi of the following formula:

0 ONE-- GONE- 7. The monoazo-dyestufi of the following formula:

GONE

OHIO Cl OH O] GONE Cl 8. The monazo-dyestuff of the following formula:

References Cited in the file of this patent UNITED STATES PATENTS Wagner Aug. 18, 1925 Grether et al. Aug. 16, 1932 Lamberz et al. Jan. 5, 1937 FOREIGN PATENTS Germany Aug. 31, 1934 Switzerland Sept. 16, 1942 

1. THE WATER-INSOLUBLE MONOAZO-DYESTUFFS OF THE FOLLOWING GENERAL FORMULA: 